Insecticidal compositions



United States Patent lNsncrrcmAL COMPOSITIONS Albert A. Schreiber, Salem, N. Y., assignor to McLaughlin Gormley King Company, Minneapolis, Minn., a corporation of Minnesota No Drawing. Application April 23, 1953 Serial No. 350,759

11 Claims. (Cl. 167-24) This invention relates to insecticides and it has particular relation to new and improved insecticidal compositions comprising, in addition to known toxicants, other ingredients, which form novel combinations of valuable properties.

In view of the rather high costs of natural pyrethrum and pyrethrum extracts and the somewhat lower, but still considerable costs of the synthetic product known under the name allethrin (allyl homologue of cinerin I) or its homologues, substances called synergist have been used for some time in combination with the pyrethroids. These synergists of widely varying chemical structures and sometimes offensive odor, which possess normally some paralyzing and lethal effect of their own, show, when combined with pyrethroids and/or other organic toxicants, a biological effect which is greater than the sum of biological effects of the individual components of such combinations. They have been added, therefore, in multiple quantities to natural and/or synthetic pyrethroids and other toxicants, in order to produce insecticidal compositions of lower cost, but of about equal biological effect in comparison with said pyrethroids and toxicants without the addition of synergists. Since the value of pyrethroids, which are still the insecticides least harmful to mammals, exists mainly in the paralyzing effect of small doses, the effect desired from addition of a synergist is mainly an increased lethality without substantial increase in the toxicity to mammals.

Other organic toxicants with high lethality, such as the well-known halogenated, and particularly chlorinated, products, e. g. the di-aryl trichloroethane derivatives, such as his (methoxy phenyl) trichloroethane, DDT and its modifications, and nuclear halogenated compounds, such as benzene hexachloride and chlordane, or mixtures thereof, are deficient in the desired quick paralyzation. By combining pyrethroids with said halogenated products, both, quick paralyzation and high lethality, have been achieved, but these combinations, without or even with the further addition of synergists, are still rather expensive and rather toxic to mammals.

Hydrocarbon toxicants, such as monoand poly-alkyl, especially methyl, naphthalenes and mixtures thereof, can be considered as standing between said groups of pyrethroids and of halogenated products.

It has to be remembered, however, that said trichloroethane derivatives differ biologically from said nuclear halogenated products by the possible cleavage of hydrochloric acid from the triehloro ethyl radicals and are thus liable to acquire the nature of an inorganic toxicant. This property can be overcome, however, for the purposes of the present invention by the addition of a strictly organic toxicant, such as the said hydrocarbon toxicants.

I have now found a group of inexpensive compounds possessing a hitherto unknown type of paralyzing effect and a very substantial synergistic lethal effect, though practically no lethal effect of their own, and a very low toxicity to mammals. Said paralyzing effect is almost instantaneous upon contact, but gradually decreases, in contrast to the gradually increasing paralyzation by pyrethroids or combinations thereof with known synergists. This spectacular behavior of the compounds in question allows of obtaining substantially higher insecticidal .elfects, since an early high paralyzation leads to substantially higher total mortality. Generally, the presence of said compounds in combinations according to the present invention, increases paralysis by toxicants deficient in paralysis and increases the lethal elfect of toxicants which are deficient in the latter.

The compounds used in combinations embodying the present invention, are oil-soluble salts of organic sulfonic acids, especially alkyl aromatic sulfonic acids, with lower nitrogen bases. The term oil-soluble is used to denote solubility in such mineral oil fractions as are commonly used for dissolving and/or diluting insecticides. Such mineral oil fractions contain, as a rule, only very minor proportions, if any, of aromatic and cyclic constituents and are available as various brands of more or less deodorized kerosene. The degree of solubility required is governed mostly by the contemplated use of the salts and the concentrations desired for finished insecticides, or for higher concentrated products for the manufacture of the former. In the latter case, products of higher solubility will be chosen than is required in the manufacture of diluted solutions. Generally, the salts of sulfonic acids with longer or more alkyl groups, show higher solubility, or even complete miscibility, with said mineral oil fractions.

Organic sulfonic acids can be obtained, broadly speaking, by sulfonating higher aliphatic olefinic compounds by adding sulfuric anhydride to a double linkage, or sulfonating aromatic compounds with the aid of sulfuric acid, with or without the aid of sulfuric anhydride. Sodium salts of said sulfonic acids, especially those of alkyl aromatic sulfonic acids, have been known and used as wetting and emulsifying agents and have been produced by sulfonation of alkyl benzenes or alkyl naphthalenes, obtainable for instance by Friedel-Crafts or vapor phase condensation, or by simultaneous alkylation and sulfonation with the aid of alkanols. In order to obtain salts of satisfactory oil-solubility, the single or multiple alkyl radicals of the aromatic nuclei should, at least jointly, contain at least 4, preferably 8-30, carbon atoms, products with single longer chains being preferred over prodnets with multiple shorter chains. It is not necessary that a certain sulfonic acid product consist exclusively of one individual compound, and such product can consist of a mixture of sulfonic acids having alkyl groups of different lengths. Such mixtures can be prepared from less refined raw materials without impairing their eifectiveness for the purposes of the present invention.

Thus, for example, a sulfonic acid mixture can be used, which contains an average of l0, 12 or 16 carbon atoms in alkyl chains of benzene or naphthalene, but in which the number of carbon atoms in the individual alkyl chains can vary by 4 to 6 carbon atoms below and above the said figures. Accordingly, the sulfonic acids, often called mahogany acids,'obtained in refining petroleum white oils, can be used in carrying out my invention.

In the compositions embodying the invention, said sulfonic acids are used in the form of their salts with lower nitrogen bases. Such nitrogen bases are ammonia and its alkylation products, such as the monoand polymethyl, ethyl, propyl, butyl, amyl and hexyl amines and alkylene amines, such as pyrrolidines and piperidines. Since salts from amines containing further substituents,

such as hydroxy or halogen substituents, are less soluble and more expensive than those from ammonia or unsubstituted lower alkyl amines, the latter are preferred. Substitution in the benzene or naphthalene nuclei, e. g. by hydroxy or halogen substituents, does not seem to materially increase the insecticidal efiect of the relative salts and tends to reduce the solubility of the latter.

Said salts can be prepared directly by reacting the freesulfonic acids with one nitrogen base, or a mixture of nitrogen bases, if desired in the presence of a solvent or coolant, such as gasoline, or higher fractions of min eral or coal tar oils, with subsequent evaporation of any water present and of the solvent or coolant, if absence of the latter in the final product is preferred. Or commercially available sodium salts are decomposed e. g. with sulfuric acid, the resulting free sulfonic acids are separated in any convenient manner, and finally reacted with the desired nitrogen base or bases. Depending on the components of the salts, the latter are viscous, honeylike liquids at room temperature or solids melting on moderate warming.

The sulfonic acid salts should be used in an amount of at least about 0.2% by weight of the final insecticidal preparations. In those cases, in which the final preparation does not contain another agent having a pronounced paralyzing effect, or a small proportion of such agent only, the amount of the sulfonic acid salt is preferably raised to 2.03.0% by weight of the final preparation.

The combinations of the sulfonic acid salts With various organic toxicants, especially those which are also soluble in said mineral oil fractions, are used in the form of homogeneous solutions, such as sprays, or aerosols. In general it is preferred to preparethe combinations of the sulfonic acid salts with the organic toxicants in the form of clear solutions in mineral oil fractions, which have the desired concentration andare free from any substantial quantity of water, beyond that occasionally occurring in the other toxicant components, and, therefore, may be 40 called anhydrous.

It has been found that mineral oil solutions of sulfonic 7 alkylamines containing alltyl groups with at least 3 car: bon atoms, preferably 3 to 5 carbon atoms, in the form of a branched chain. For example, while in combinations with allethrin the lethality of the latter, for instance on roaches, can be doubled'by the addition of an ammonium salt, it can be increased to 6 or 7 times that of allethrin alone, by the addition of a salt of an amine, such as propyl, butyl or amyl amine. Therefore, specific salts can be easily chosen in accordance with the intended use of the final preparations.

In testing the preparations according to the invention outdoors under various conditions, it has been found that their effect is much less alfected by low humidity and high temperatures than that of preparations made from equivalent toxicants under equal conditions, but in the absence of sulfonic acid salts used according to the invention. Therefore, very satisfactory results are obtained with the compositions of the invention even in arid regions.

The following specific examples serve to illustrate the nature of this invention, without limiting the latter thereto.

Milligrams Toxieant, Milligrams Sulionic acid salt pyrethrins isc-propylamine salt of 500 dodecyl benzene monosulfonic acid.

ammonium salt of dodecyl benzene monosulfonic acid.

dimethylaminc salt of dodecyl benzene monosulfonic acid.

trimethylamine salt of dodecyl benzene monosulfonic acid.

ethylamine salt of dodecyl benzene monosulionic acid.

allylaminc salt of dodecyl benzene monosulfonic acid.

isc-prcpylamine salt of dodecyl benzene monosulfonic acid iso-butylaminc salt of dodecyl benzene monosulfonic acid.

iso-amylamine salt of dodecyl benzene monosulfonic acid.

n-hexylantine salt of dodecyl benzene monosultonic acid.

2-ethylhexyla-mine salt of dodecyl benzene monosulfonic acid.

choline salt of dodecyl benzene mouosulfonic acid.

pyrrclidine saltof dodecyl benzene nionosulfouic acid.

piperidine salt of dodecyl benzene monosulfonic ttClCt.

ammonium salt of a mixtlllG 0f Gag-C23 alkyl benzene monosulfonic acid.

iso-propylarnine salt of a mixture of aikyl aryl sulfonic acids from the refining or" white oil (mahogany acid).

ammonium salt of di-isopropyl naphthelene monosulfonic acid.

isc-propylamine salt of oleic ester of isethionic acid.

ammonium salt of dicotylestcr ei snltosuccinic {allethriu allethrin 100 VII d0 100 VIII do IX do 500 XIIIQ.. 100

XIV"... 100. 500

XVI. 100 500 XVII .-d0 100 XVIII. d0 100 500 XIX d0 100 500 50 XXI. methylated 4, 000

naphthalenes.

Milligrams (a) Pyrethrins 50 (b) Pyrethrins (0T1) 100 (c) Allethrin 50 (d) Allethrin 100 (c) Methylated naphthalenes 4000 (f) Iso-propylamine salt of dodecyl benzene monosulfonic acid 500 g) Ammonium salt of a mixture of C -C alkyl benzene sulfonic acids 500 The above described solutions l-XXI and (a)-(g) were tested with regard to their effect on flies according to the standard Peet Grady method on large groups of flies as described in'Soap, Blue'Book, 1952, p. 255. The results are shown in the following Table I. V

Table I Table II Percent paralysis Above r Percent above or in- Percent below Ml. Mortality below Solution mortality individual Solution Dosage individual 6 in 24 hours 0. T. I. O. T. I.

3 5' 5 24 hrs. 48 hrs.

94 96 96 22 0.4 78 83-85 98 99 99 -46 0.4 5 16 -70 94 95 97 30 0.4 4 13 -73 96 98 99 50 0.4 0 0 -85 65 66 68 21 0.5 9 0 -83 66 66 50 8 0.4 0 0 86 67 58 42 3 0.4 5 8 -77 99 99 99 65 0.4 37 77 97 98 99 86 0.4 88 91 +6 96 97 99 79 0.4 66 86 -2 97 98 99 85 0.4 82 -13 98 99 99 86 0.4 31 57 3o 96 97 100 82 0. 4 69 95 +10 98 99 100 84 0.4 51 69 -22 97 98 99 75 0.4 39 62 -30 97 98 100 72 0.4 42 64 -19 97 98 99 89 0.4 40 68 -13 96 97 99 72 0.4 80 82 -1 94 96 99 71 0.4 80 95 +10 97 98 99 91 0.4 65 98 +21 98 98 99 84 99 99 99 76 96 98 99 73 -31 97 97 99 71 The poss1b1l1ty of replacing large amounts of pyrethnns 8g 3g 3g Z3 13% in aerosols by combming allethrln wlth one of the salts 96 97 100 99 58 used according to the present invention is shown by the 97 95 99 91 55 25 followmg tests, whlch were carried out by the C. S. M. A.

Aerosol Test Method as described in Soap, Blue Book, EXAMPLE XXII 1952, p. 251, against the standard T. O. T. A. as indi- 100 milligrams of allethrin, 4300 milligrams of methylcated.

Table III iso-propyl- Paralysis, Perpiperamine salt cent Mortal- Pyreth- Allethonyl DDT Sovacide of dodecyl ity,

rins rin bubenzene percent toxlde mono-sul- 5 10 15 24 hrs. ionic acid Percent of Total ated naphthalenes and 500 milligrams of the iso-propyl- The above concentrations denote the percentages of amine salt of dodecyl benzene monosulfonic acid, are disactive ingredients in the finished aerosol spray consisting solved in deodorized kerosene to a solution of 100 mls. of 42.5% each of Freon 11 and Freon l2 and 15% of concentrate in which latter the balance of the active in- EXAMPLE XXIII gredients stated and the said percentage of 15 consists 300 milligrams of chlordane and 500 milligrams of the decdmized kerlseneiso-propylamine salt of dodecyl benzene monosulfonic acid are dissolved in deodorized kerosene to a solution of 100 mls. An area in the nei ghborhood of hog pens in Arizona g g g g igg sg ifgga g g g g f gg was regularly sprayed with the aid of a fogging machine :F are e o wlth a spray containing 0.2% by weight (0.25% W/v, i. e. 0.25 grams per 100 mls.) of pyrethrins, and the on irf-ifi 3L1? riii ivifiiii i 1; 3312311232 effect We checked with the aid P slamming) fly method of C S M A as described in Soap vol. 22 p. traps gwmg the of survmng files In order M5 (1946) i 'the"above described solutions I, 5 to reduce the cost of this treatment the area was sprayed first with DDT and after the flies became resistant to VIi, IX, XII, XIII, XIV, XV, XX, XXI, XXH, XXIII, (e), (1.) (g), as well as the following 801w sprays contalmng up to 10% DDT, with 10% chlordane,

EXAMPLE XXIV tions' 5% lindane and 3% parathion. In each case the re- Solmion (h) .43000 milligrams of methylated naphduction in i fly poplilation could f. be increated thalenes dissolved in deodorized kerosene to 100 mls. soluyond companson to the Ongmal reducnon of tion; about 92 A: The area was then sprayed by the same Solution (i).300 milligrams of chlordane dissolved in machlne Wlth p y 001181811118 26% (W/v, 1. e. decdorized kerosene to 0 1 Solution 0.26 grams per 100 mls.) of allethrm, 1.3% of the ethyl- The results of the tests are shown in the following heXyl di-keto PYIIOlidiIJe according t0 Patcnt Table H. 2,476,512 and 1.3% of the iso-propylamine salt of dodecyl benzene mono-sulfonic acid in deodorized kerosene, whereby the reduction in the fly population reverted to 94 and 95% Without noticeable decrease within months.

EXAMPLE XXV 1000 milligrams of bis(p-methoxyphenyl) trichloroethane (methoxychlor), 8000 milligrams of methylated naphthalenes and 2000 milligrams of the iso-propylamine salt of dodecyl benzene monosulf o nic a ci d, are dissolved in deodorized kerosene to a solution oflOO mls.

When tested in the manner statediaboye in connection with Table I, the percent paralysisin- 3", 5 and was found to be 99, 100, 100, respectively; thepercent mortality in 24 hours was found to be 100, 64 above individual O. T. I. .1 7'

When tested in the manner describedabove in connection with Table II, dosage 0.4 -ml., the percent mortality in 24 hours as well as in 4 8ihours,fvvas found to be 100, above individual 0. T. I." a e a i in the present specification and claims, the term allethrin denotes the synthetic analog of Cinerin I, i. e. d,l-2-allyl-4-hydroxy-3-methyl-2-cyclopentene 1 one esteriiied with a mixture of cisand trans chrysanthemum rnonc-carboxylic acids, quantities stated corresponding to 100% of the said esters from commercial 90% material as analyzed by hdrogenolysis or other suitable method.

The term methylated naphthalenes denotes commercial mixtures of mono-, diand trimethyl naphthalenes, with a preponderating percentage of dimethyl naphthalenes, of which Sovacide (PD544C) is a commercial brand.

The term piperonyhbutoxide denotes the commercial product consisting mainly of alpha-(2-(2-butoXyeth0Xy)- ethoxy -4,5-methylenedioXy-2-propyl-toluene.

The terms mahogany acid and mahogany sulfonates denote the mixture of sulfonic acids, also called petroleum sulfonates, occurring as byproducts in the removal of unsaturated hydrocarbons from petroleum fractions with the aid of strong sulphuric acid, as for example in the production of white oils.

The terms 0. T. I. and T. O. T. A. stand for Oflicial Test Insecticide and Tentative Ofiicial Test Aerosol and the standards obtained therewith, Soap, Blue Book being published as Soap and Sanitary Chemicals, Blue Book and Catalog Edition, by the MacNair-Dorland Company, New York.

The term organic toxicant is used herein to denote and include organic toxicants of the type of the pyrethroids, as exemplified by pyrethrins and allethrin, aromatic toxicants such as alkylated, especially methylated, naphthalenes, nuclear polychlorinated cyclic cornpounds, such as benzene hexachloride, polychloro endomethylene hydronaphthalenes and cyclopentadienes, such as chlordane, as well as the combinations of aromatic toXicants, such as the methylated naphthalenes, with di-phenyl trichloro ethane compounds, such as DDT and methoxychlor (1,1,- l-trichloro-2,2bis (p-methoxyphenyl) ethane) which latter, owing to the possible cleavage of hydrochloric acid from the aliphatic radical and apparent difierent biological effect, are liable to be considered as inorganic toxicants in contrast to the said nuclear polychlorinated compounds. The said different effect can be overcome, however, in the said combination with a strictly organic toxicant.

It will be understood from the above description, examples and explanations that my invention is not limited to the specific, individual materials, proportions and other specific details specifically described above and can be carried out with various modifications in commercial practice. For example, commercially available sulfonic V acids, such as dodecyl benzene sulfonic acid may be replaced by decyl or hexadecyl benzene sulfonic acids and di-isopropyl naphthalene sulfonic by di-butyl naphthalene sulfonic acid or the corresponding sulfonic acids ob- The di-octyl ester of sulfosuccinic acid may be replaced by the corresponding dibutyl, -amyl or hexyl esters, and sulfonic acids may be used as are obtained by the sulfonation of "olefines containing from 8-16, preferably at least 12, carbon atoms with aceto sulphuric acid, chlorosulphonic acid, fuming sulphuric acid in an inert solvent, or addition compounds of sulphuric anhydride and ethers. If convenient the salts used according to the present invention can be prepared from mixtures of the different sulphonic acids, and also mixtures of the different bases can be used while taking care that approximately accurate neutralization is obtained, so that the resulting products are practically neutral or show, in Water, only very little alkalinity or acidity from their production or owing to diflering ionization constants of the components. In most cases, the salts of the rather volatile, lower nitrogen bases will be preferred for commercial use.

The term DDT is used in the present application to denote the compound 1,1,l-trich1oro-2,2-bis (p-chlorophenyl)ethane and the term chlordanelis used to denote the compound l,2,4,5,6,7,8,8-octachloro-2,3,3a,4,7,7ahexahydro-4,7-methanoindene. The term allethrin is the common name. given by the Interdepartmental Committee on Pest Control to a synthetic ester, the dl 2-allyl- 4-hydroXy-3-methyl-2-cyclopenten-l-one ester of the mixture of cis and trans dl-chrystanthemum carboxylic acid, and is used in the present application to denote said compound.

What is claimed is:

1. Anhydrous insecticidal composition comprising, dissolved in a kerosene type mineral oil fraction, a pyrethroid and from about 2 to 10 times its weight of a nitrogen base salt, selected from the group consisting of --NH., and amines containing up to 8 carbon atoms, of an alkyl aryl monosulfonic acid, whose alkyl groups contain 6-30 carbon atoms and whose aryl groups are selected an alkyl benzene monosulfonic acid, whose alkyl groups contain 8-28 carbon'atoms.

3. Anhydrous insecticidal composition comprising, dissolved in a kerosene type mineral oil fraction, a pyrethroid and from about 2 to 10 times its weight of a nitrogen base salt, selected from the group consisting of -NH and amines containing up to 8 carbon atoms, of

an alkyl benzene monosulfonic acid, whose alkyl groups contain 8-12 carbon atoms.

4. Anhydrous insecticidal composition comprising, dissolved in a kerosene type mineral oil fraction, a pyrethroid and from about 2 to 10 times its .weight of an alkylamine salt, containing in said alkylamine up to 8 carbon atoms, of an alkyl benzene monosulfonic acid, whose alkyl groups contain 812 carbon atoms.

5. Anhydrous insecticidal composition comprising, dissolved. in .a'kerosene type mineral oil fraction, pyrethrins and from about 2m 10 times their weight of an alkylamine salt, containing in said alkylamine up to 8 carbon atoms, of an alkyl benzene monosulfonic acid, whose alkyl groups contain 8-12 carbon atoms.

6. Anhydrous insecticidal composition comprising, dissolved in a kerosene type mineral oil fraction, allethrin and from about 2-10 times its weight of a nitrogen base salt, selected from the group consisting of NH, and amines containing up to 8 carbon atoms, of any alkyl benzene monosulfonic acid, whose alkyl groups contain 8-28 carbon atoms.

7. Anhydrous insecticidal composition comprising, dissolved in a kerosene type mineral oil fraction, allethrin and from about 2-10 times its weight of an alkylamine salt, said alkylamine containing 2-6 carbon atoms, of an alkyl benzene monosulfonic acid, whose alkyl groups contain 8-12 carbon atoms.

8. Anhydrous insecticidal composition comprising, dissolved in a kerosene type mineral oil fraction, allethrin and from about 2-10 times its Weight of an alkylamine salt, said alkylamine containing 3 carbon atoms, of an alkyl benzene monosulfonic acid, whose alkyl groups contain 8-12 carbon atoms.

9. Anhydrous insecticidal composition comprising, dissolved in a kerosene type mineral oil fraction, allethrin and from about 2-10 times its weight of the isopropylamine salt of an alkyl benzene monosulfonic acid, whose alkyl groups contain 8-12 carbon atoms.

10. Anhydrous insecticidal composition comprising, dissolved in a kerosene type mineral oil fraction, allethrin and from about 2-10 times it weight of the isopropylamine salt of dodecyl benzene monosulfonic acid.

11. Anhydrous insecticidal composition comprising, dis- 10' solved in a kerosene type mineral oil fraction, allethrin and from about 2-10 times it weight of a propylamine salt of a mahogany acid.

References Cited in the file of this patent UNITED STATES PATENTS 2,205,950 Flett June 25, 1940 2,247,365 Flett July 1, 1941 2,283,199 Flett May 19, 1942 2,538,724 Hass et al. Jan. 16, 1951 2,607,796 Schecter et al. Aug. 19, 1952 2,696,453 Sanders Dec. 7, 1954 2,731,338 Fike Jan. 17, 1956 FOREIGN PATENTS 463,544 Great Britain Mar. 30, 1937 OTHER REFERENCES Campbell et al.: J. of Econ. Entom., December 1934,

Brown: A. W. A., Insect Control by Chemicals, 1951, pp. 26, 115-117, 486, and 694.

Brown: A. W. A., Insect Control by Chem., 1951, pp. 207-209. 

1. ANHYDROUS INSECTICIDAL COMPOSITION COMPRISING, DISSOLVED IN A KEROSENE TYPE MINERAL OIL FRACTION, A PYRETHROID AND FROM ABOUT 2 TO 10 TIMES ITS WEIGHT OF A NITROGEN BASE SALT, SELECTED FROM THE GROUP CONSISTING OF -NH4 AND AMINES CONTAINING UP TO 8 CARBON ATOMS, OF AN ALKYL ARYL MONOSULFONIC ACID, WHOSE ALKYL GROUPS CONTAIN 6-30 CARBON ATOMS AND WHOSE ARYL GROUPS ARE SELECTED FROM THE GROUP CONSISTING OF BENZENE AND NAPHTHALENE. 